Stereochemistry of Octahedral cis-Tetrafluoro Titanium Complexes with Ph2P(O)CH(Me)CH2C(O)Et Enantiomers in CH2Cl2


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Abstract

The complex formation of TiF4 with the phosphorylated ketone Ph2P(O)CH(Me)CH2C(O)Et (L), containing an asymmetric carbon atom in the aliphatic hydrocarbon group and representing a racemic mixture of enantiomers, was studied by 19F{1H} and 31P{1H} NMR spectroscopy. The composition of complexes formed in the solution was determined; analysis of the 19F NMR spectra resorting to the heterotropicity concept was used to assign the resonance lines to two chiral optically active racemic and meso-stereoisomers of cis-TiF4L2. The configurations of enantiomers of the monodentate ligand coexisting in the coordination sphere were found to have a crucial effect on the axial fluorine atoms of mixed octahedral cis-tetrafluoro d0 transition metal complexes. A new efficient method was developed for the synthesis of ligand L.

About the authors

E. G. Il’in

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: eg_ilin@mail.ru
Russian Federation, Moscow, 119991

A. S. Parshakov

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow, 119991

V. I. Privalov

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow, 119991

E. I. Goryunov

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow, 119991

I. B. Goryunova

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow, 119991

E. E. Nifant’ev

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: eg_ilin@mail.ru
Russian Federation, Moscow, 119991

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